CN108439845A - A kind of cement grinding aid of high efficiency, low cost and preparation method thereof - Google Patents
A kind of cement grinding aid of high efficiency, low cost and preparation method thereof Download PDFInfo
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- CN108439845A CN108439845A CN201710083082.4A CN201710083082A CN108439845A CN 108439845 A CN108439845 A CN 108439845A CN 201710083082 A CN201710083082 A CN 201710083082A CN 108439845 A CN108439845 A CN 108439845A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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- Structural Engineering (AREA)
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Abstract
The invention discloses a kind of cement grinding aids of high efficiency, low cost, by following material composition：6 8wt% of triethanolamine, 3 5wt% of molasses, 4 8wt% of polyether polyol, 22 35wt% of paper pulp wastewater, 7 10wt% of sodium thiosulfate, 1.5 3wt% of anhydrous sodium acetate, 1 6wt% of air entraining agent, 3 6wt% of multi-hydroxy carboxy acid, surplus is distilled water.Wherein the air entraining agent is wooden sodium sulfonate or triterpenoid saponin, and the multi-hydroxy carboxy acid is the product aoxidized by polysaccharide, and the paper pulp wastewater is handled by resins exchange, removes chlorion therein, and Baume degrees is 16~20 ° of B é, pH 7.The waste water of papermaking enterprise has not only been effectively treated using paper pulp wastewater as raw material in the cement grinding aid of the present invention, also reduces the production cost of grinding aid, and multi-hydroxy carboxy acid is added, and reduces the ratio of mud, improves strength of cement, ensures the quality of cement.
Description
Technical field
The present invention relates to the additives in a kind of cement production process, more particularly to a kind of cement efficiently, inexpensive
Grinding aid；Additionally relate to a kind of preparation method of cement grinding aid.
Background technology
In cement production process, grinding is one of important procedure, it is by mechanical means by clinker, retarder
The granularity being only suitable for other adjusting material powders, to meet the requirement of cement slurry condensation, hardening.In grinding process, by
In frequently colliding and rubbing between material and abrasive body in ball mill, will produce a large amount of electrostatic, so as to cause material with grind
Electrostatic Absorption is generated between mill body, material is made to wrap abrasive body and mill interior lining panel, partition panel, causes mill efficiency to decline, object
Material blocks, and even can influence being normally carried out for powder-grinding process when serious.
And cement grinding aid is indispensable auxiliary material in cement industry now, and a small amount of cement is mixed in cement
Grinding aid can improve material particles mobility by its surface-active and charge peptizaiton, to improve grinding fineness efficiency,
Energy consumption is reduced, while will not also damage the performance of cement.
There are many cement grinding aids to use for cement producer, and by classification of chemical structure, cement grinding aid can be divided into three
Kind：It polymerize organic salt grinding aid, polymer-inorganic salt grinding aid and complex chemical compound grinding aid.Cement grinding aid production used at present
Product belong to greatly organic matter surface active material.Due to the grinding aid higher price of one-component, and its performance is single, uses
Effect is not very ideal, and in recent years, complex chemical compound grinding aid becomes people's point of research, and is widely used in cement grinding
In sequence.
Cement grinding aid can be divided into two kinds of powder and liquid according to its state.The component of powdery cement grinding aid is logical
Often it is stearates, colloidal silicon dioxide, aquadag, carbon black, flyash, gypsum etc..The liquid of mass selling in the market
Grinding aid, most of compounded by triethanolamine, glycerine, urea, soda ash etc. and other chemical materials
Wherein, powdery cement grinding aid needs the amount added relatively high, and powdery cement grinding aid is mostly multiple with technical pure
It is primary raw material to close organic salt and inorganic salts, the chloride ion in cement content produced can be caused higher, it is difficult to reach new state
Grinding aid addition should be wanted no more than 0.5% and chloride ion in cement content of cement weight no more than 0.06% in family's standard
It asks.And the salt ion content of liquid cement grinding additive is low, and its addition is convenient, therefore liquid cement grinding additive is in current water
Application in mud production is than wide.But there is also following deficiencies for existing liquid cement grinding additive：Grinding aid product is a large amount of
Using triethanolamine, cause grinding aid of high cost；Potent fruit unobvious are carried to the cement of large dosage lime stone；It is built containing having an impact
The harmful components such as the chlorion of object service life.
Paper pulp wastewater is the liquid debris that papermaking enterprise generates, and is such as discharged into soil or water source without processing, meeting
The eutrophication for causing water and soil, seriously affect with soil water quality, lead to plant, animal dead, and then can also threaten people
Class health.The existing method that paper pulp wastewater is handled, although its harm to environment can be reduced, processing cost height,
A large amount of soils can also be occupied and carry out waste accumulation, a large amount of manpower financial capacities is needed to safeguard.
Invention content
It is an object of the invention to overcome shortcoming in the prior art, a kind of cement efficiently, inexpensive is provided and is helped
Grinding agent.
The purpose of the present invention is achieved through the following technical solutions：
A kind of cement grinding aid of high efficiency, low cost, by following material composition：
Triethanolamine 6-8wt%, molasses 3-5wt%, polyether polyol 4-8wt%, paper pulp wastewater 22-35wt% are thio
Sodium sulphate 7-10wt%, anhydrous sodium acetate 1.5-3wt%, air entraining agent 1-6wt%, multi-hydroxy carboxy acid 3-6wt%, surplus are distillation
Water；Wherein the air entraining agent is wooden sodium sulfonate or triterpenoid saponin, and the multi-hydroxy carboxy acid is aoxidized to obtain by polysaccharide
Product, the paper pulp wastewater are handled by resins exchange, remove chlorion therein, the Baume degrees of the paper pulp wastewater is 16
~20 ° of B é, pH 7.
Preferably, the multi-hydroxy carboxy acid is citric acid.
The present invention also provides a kind of methods for the cement grinding aid preparing above-mentioned high efficiency, low cost, and the method includes as follows
Step：
(a) paper pulp wastewater for taking paper mill production discarded, removes chlorion therein by ion exchange resin, then surveys
Determine pH value, pH adjusting agent is added to pH=7, it is 16~20 ° of B é finally to adjust its Baume degrees；
(b) according to the dosage of each substance in the cement grinding aid of above-mentioned high efficiency, low cost, each substance of precise is spare；
(c) triethanolamine, polyether polyol are added in suitable distilled water, magnetic force while being warming up to 40~50 DEG C
It stirs evenly, adds sodium thiosulfate and be uniformly dissolved, be eventually adding molasses, stir evenly and maintain 40~50 DEG C for use；
(d) it takes anhydrous sodium acetate and multi-hydroxy carboxy acid to be added in remaining distilled water, air entraining agent is added after stirring, stir
Uniformly, it is eventually adding paper pulp wastewater, stirs 30min；
(e) mixture that step (d) obtains is added to while stirring in the mixture that step (c) obtains, magnetic agitation
20~30min.
Preferably, pH adjusting agent is acetic acid or ammonium hydroxide.
Preferably, by the way that distilled water or evaporation and concentration is added, the Baume degrees of paper pulp wastewater is adjusted.
In the cement grinding aid of high efficiency, low cost provided by the present invention, triethanolamine, molasses and polyether polyol and
Paper pulp wastewater all plays grind -aiding effect, and wherein hydramine is good surfactant, can efficiently reduce powder process
The charge of middle generation inhibits the caking phenomenon between material and milling apparatus in process of lapping.
The present inventor is by long term test and improves discovery, paper pulp wastewater is used for cement process, not only
Grinding effect can be significantly improved, can also inhibit to grind interior bag ball phenomenon, and the concentration of paper pulp wastewater, pH value and remaining
The cooperation of other grinding aid materials can generate significant impact to its grinding-aid effect.When the grinding aid agent concentration worked good is excessive, can lead
Material reunion caking, reason for that in process of lapping is caused mainly since grinding aid agent concentration is excessive, to be not easy to be well-dispersed in object
In material；And when the grinding aid agent concentration worked good is too small, then grinding effect is promoted less, or even caking can be aggravated, blocked now
The generation of elephant.By careful studying, find with Baume degrees to be the paper pulp wastewater that 16~20 ° of B é, pH are neutrality to be raw material, with three second
The material that hydramine, honey etc. routinely play abrasive action rationally coordinates, and milling apparatus 3-5 hours are added in obtained grinding aid
Afterwards, the caking of milling apparatus, clogging substantially reduce, the work that milling apparatus can be steady in a long-term.
But it is different according to technique used in papermaking enterprise, the property of paper pulp wastewater is also not quite similar, in addition, in association with pulp bleaching
It needs to use a large amount of chlorion in the process, and influence of the chlorion to cement is fatal, as destroyed in armored concrete
Passivation layer, accelerating corrosion reaction, can also form primary battery and further speed up corrosion.Therefore, paper is adjusted by the way that pH adjusting agent is added
The acid-base property of pulp waste water, is handled by resins exchange and removes chlorion, and the cement grinding aid ensured will not generate cement
It influences.
Inventor also found, the multi-hydroxy carboxy acid that polysaccharide aoxidizes, compared to the auxiliary agent of existing cement grinding aid,
It is more positive to the produced effect of cement process.The multi-hydroxy carboxy acid aoxidized by polysaccharide is added in grinding aid,
In use, the ratio of mud reduces the cement of production arrived, and reduces influence of the water to cement performance, and improves cement, mixes
The early anti pressured intension and early stage yield strength of solidifying soil product.Relative to the quality of cement, the addition of multi-hydroxy carboxy acid is less,
Such as in 0.001%-2%, wherein multi-hydroxy carboxy acid is especially best with the effect of citric acid.
In the cement grinding aid of high efficiency, low cost provided by the present invention, air entraining agent be wooden sodium sulfonate or triterpenoid saponin,
The water consumption that cement normal consistency can also be reduced arranges in pairs or groups with multi-hydroxy carboxy acid, can not only carry and coordinate height together with other compositions
Grinding effect also improves the performance of cement products.
In the cement grinding aid of high efficiency, low cost provided by the present invention, sodium thiosulfate and anhydrous sodium acetate play excitation
Agent acts on, and can promote the premature cure of cement, and improve intensity.
The waste paper pulp wastewater of papermaking enterprise is added to the effect that grinding aid is played in grinding aid by the present invention, not only effectively
The process problem of the paper pulp wastewater of solution, also makes full use of waste, turns waste into wealth, while other grinding aid materials three are greatly decreased
The use of ethanol amine etc., reduces production cost.It has also been found that the grinding aid of multi-hydroxy carboxy acid is added, grinding process is not only helped
Be smoothed out, can also significantly reduce the ratio of mud, improve cement, the early anti pressured intension of concrete product and early stage surrender it is strong
Degree and other auxiliary agents.It is additionally added air entraining agent, sodium thiosulfate equal excitation agent in the grinding aid of the present invention, further increases its grinding
The performance of performance and cement product.
The cement grinding aid of the present invention, by being pre-processed to raw material, and selects various raw materials with caution, control wherein chlorine
The content and alkali content of ion, have no toxic side effect, and meet the relevant criterion of country and industry.Also, in conjunction with different material
Synergistic effect and its influence degree to process of lapping, cement products performance, various raw materials contains in reasonable disposition grinding aid
Amount, the effect for giving full play to grinding aid, improving cement performance.
Specific implementation mode
In order to preferably explain the present invention, the present invention is explained and illustrated by detailed description below.
A kind of cement grinding aid of high efficiency, low cost, by following material composition：Triethanolamine 6-8wt%, molasses 3-
5wt%, polyether polyol 4-8wt%, paper pulp wastewater 22-35wt%, sodium thiosulfate 7-10wt%, anhydrous sodium acetate 1.5-
3wt%, air entraining agent 1-6wt%, multi-hydroxy carboxy acid 3-6wt%, surplus are distilled water；Wherein the air entraining agent is lignosulfonic acid
Sodium or triterpenoid saponin, the multi-hydroxy carboxy acid are the products aoxidized by polysaccharide, and the paper pulp wastewater is handed over by resin
Processing is changed, removes chlorion therein, the Baume degrees of the paper pulp wastewater is 16~20 ° of B é, pH 7.
The preparation method of the cement grinding aid of above-mentioned high efficiency, low cost includes the following steps：
(a) paper pulp wastewater for taking paper mill production discarded, removes chlorion therein by ion exchange resin, then surveys
Determine pH value, pH adjusting agent is added to pH=7, it is 16~20 ° of B é finally to adjust its Baume degrees；
(b) according to the dosage of each substance in the cement grinding aid of above-mentioned high efficiency, low cost, each substance of precise is spare；
(c) triethanolamine, polyether polyol are added in suitable distilled water, magnetic force while being warming up to 40~50 DEG C
It stirs evenly, adds sodium thiosulfate and be uniformly dissolved, be eventually adding molasses, stir evenly and maintain 40~50 DEG C for use；
(d) it takes anhydrous sodium acetate and multi-hydroxy carboxy acid to be added in remaining distilled water, air entraining agent is added after stirring, stir
Uniformly, it is eventually adding paper pulp wastewater, stirs 30min；
(e) mixture that step (d) obtains is added to while stirring in the mixture that step (c) obtains, magnetic agitation
20~30min.
In order to control the content of chlorion and alkali in cement grinding aid, selection uses not chloride ion-containing and is easy to the vinegar removed
Acid or ammonium hydroxide adjust pH；And by the way that distilled water or evaporation and concentration is added, the Baume degrees of paper pulp wastewater is adjusted, other will not be introduced
Harmful components.
Embodiment 1
The paper pulp wastewater in paper mill is taken, it is alkalinity after measured, and main component is lignin derivative, organic salt, vulcanization
Sodium, sodium hydroxide, hypochlorite etc..Paper pulp wastewater is handled by 732 cation exchange resins first and removes chlorion therein,
Further according to its pH value, acetic acid is added dropwise in a manner of titration to pH=7, distilled water adjustment is added in the paper pulp wastewater that titration is completed
Its Baume degrees is 16 ° of B é；
Weigh triethanolamine 6kg, molasses 3kg, polyether polyol 5kg, processed paper pulp wastewater 30kg, sodium thiosulfate
7kg, anhydrous sodium acetate 3kg, wooden sodium sulfonate 4kg, citric acid 6kg, distilled water 36L；
Fetch water 10L, load weighted triethanolamine, polyether polyol is added thereto, magnetic force while being warming up to 40 DEG C
It stirs evenly, adds sodium thiosulfate and be uniformly dissolved, be eventually adding molasses, stir evenly and maintain 40 DEG C for use, be denoted as
Mixture A1；
Anhydrous sodium acetate and multi-hydroxy carboxy acid are added in remaining distilled water again, the wooden sulphur of air entraining agent is added after stirring
Sour sodium, stirs evenly, and is eventually adding paper pulp wastewater, and stirring 30min is denoted as B1 to uniform；
Under agitation, B1 is added in A1, magnetic agitation 30min is up to cement grinding aid S1.
Embodiment 2
Operated with embodiment 1 identical, wherein difference is：Triethanolamine 8kg, molasses 5kg, polyether polyol 7kg are weighed,
Processed paper pulp wastewater 24kg, sodium thiosulfate 10kg, anhydrous sodium acetate 2kg, triterpenoid saponin 2kg, citric acid 4kg, distillation
Water 38L.
According to the preparation method of embodiment 1, cement grinding aid S2 is obtained.
Embodiment 3
Take the paper pulp wastewater in paper mill, after measured its for acidity, main component be organic acid, sulphite, vulcanized sodium with
And free chloro ion.It is first diluted with water the paper pulp wastewater, is filtered to remove wherein insoluble matter and bulky grain, then pass through amberlite
Fat processing removes free chlorine therein, and ammonium hydroxide is then added dropwise in a manner of titration again to pH=7, by the paper pulp wastewater of titration completion
It is concentrated by evaporation, it is 20 ° of B é to adjust its Baume degrees；
Weigh triethanolamine 7kg, molasses 4kg, polyether polyol 4kg, processed paper pulp wastewater 33kg, sodium thiosulfate
8.5kg, anhydrous sodium acetate 1.5kg, wooden sodium sulfonate 2kg, triterpenoid saponin 2kg, citric acid 3kg, distilled water 35L；
Fetch water 12L, load weighted triethanolamine, polyether polyol is added thereto, magnetic force while being warming up to 50 DEG C
It stirs evenly, adds sodium thiosulfate and be uniformly dissolved, be eventually adding molasses, stir evenly and maintain 50 DEG C for use, be denoted as
Mixture A3；
Anhydrous sodium acetate and multi-hydroxy carboxy acid are added in remaining distilled water again, air entraining agent is added after stirring, is stirred
Uniformly, it is eventually adding paper pulp wastewater, stirring 30min is denoted as B3 to uniform；
Under agitation, B3 is added in A3, magnetic agitation 30min is up to cement grinding aid S3.
Embodiment 4
Cement grinding aid S1, S2, S3 that identical cement raw material and above-described embodiment 1-3 are obtained are chosen, and in the market
A certain ordinary cement grinding aid D1, is tested.Test result such as table 1.
In process of lapping, grinding aid S1, S2, the S3 obtained using the present invention can effectively improve grinding efficiency, grind
Without phenomena such as blocking during mill.Milling apparatus is observed after grinding, with the milling apparatus of S1, S2, S3, surface
Caking situation is better than the milling apparatus using D1 as grinding aid.As a result as follows.
Table 1
Have this as it can be seen that the present invention cement grinding aid, can be effectively ensured being smoothed out for grinding process, inhibit ground
Phenomena such as caking in journey and blocking, and material particular diameter smaller after grinding.Additionally aid cement, concrete product early strength
Raising, it helps reduce setting time.
Claims (5)
1. a kind of cement grinding aid of high efficiency, low cost, which is characterized in that the cement grinding aid is by following material composition：Three second
Hydramine 6-8wt%, molasses 3-5wt%, polyether polyol 4-8wt%, paper pulp wastewater 22-35wt%, sodium thiosulfate 7-
10wt%, anhydrous sodium acetate 1.5-3wt%, air entraining agent 1-6wt%, multi-hydroxy carboxy acid 3-6wt%, surplus are distilled water；Wherein
The air entraining agent is wooden sodium sulfonate or triterpenoid saponin, and the multi-hydroxy carboxy acid is the product aoxidized by polysaccharide, institute
The paper pulp wastewater stated is handled by resins exchange, removes chlorion therein, the Baume degrees of the paper pulp wastewater is 16~20 ° of B
é, pH 7.
2. a kind of cement grinding aid of high efficiency, low cost according to claim 1, which is characterized in that the multi-hydroxy carboxy acid
It is citric acid.
3. a kind of method for the cement grinding aid preparing the high efficiency, low cost described in any one of claim 1-3, feature exist
In described method includes following steps：
(a) paper pulp wastewater for taking paper mill production discarded, removes chlorion therein by ion exchange resin, then measures pH
PH adjusting agent is added to pH=7 in value, and it is 16~20 ° of B é finally to adjust its Baume degrees；
(b) in the cement grinding aid of high efficiency, low cost described in accordance with the claim 1 each substance dosage, each substance of precise
It is spare；
(c) triethanolamine, polyether polyol are added in suitable distilled water, magnetic agitation while being warming up to 40~50 DEG C
Uniformly, it adds sodium thiosulfate to be uniformly dissolved, is eventually adding molasses, stir evenly and maintain 40~50 DEG C for use；
(d) it takes anhydrous sodium acetate and multi-hydroxy carboxy acid to be added in remaining distilled water, air entraining agent is added after stirring, stirring is equal
It is even, it is eventually adding paper pulp wastewater, stirs 30min；
(e) mixture that step (d) obtains is added to while stirring in the mixture that step (c) obtains, magnetic agitation 20~
30min.
4. according to the method described in claim 3, it is characterized in that, the pH adjusting agent is acetic acid or ammonium hydroxide.
5. according to the method described in claim 3, it is characterized in that, by the way that distilled water or evaporation and concentration is added, adjustment paper pulp is useless
The Baume degrees of water.
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| CN110615637A (en) * | 2019-09-10 | 2019-12-27 | 广西喜华园建材科技有限公司 | Efficient cement grinding aid and preparation method thereof |
| CN115196904A (en) * | 2022-08-29 | 2022-10-18 | 襄阳安格尔建材科技有限公司 | Cement raw material grinding aid and preparation method thereof |
| CN115196904B (en) * | 2022-08-29 | 2023-08-22 | 襄阳安格尔建材科技有限公司 | Cement raw material grinding aid and preparation method thereof |
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Effective date of registration: 20190529 Address after: 362200 Building C 9F905, Haiming Cultural Industry City, Jinjiang, Meiling Street, Jinjiang City, Quanzhou City, Fujian Province Applicant after: Fujian Chaoxu New Energy Technology Co., Ltd. Address before: 362201 10th Floor, Xingda Building, Zhushuxia Community, Meiling Street, Jinjiang City, Quanzhou City, Fujian Province Applicant before: QUANZHOU CHAOXU NEW ENERGY TECHNOLOGY CO., LTD. |
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Application publication date: 20180824 |